Fates of Hydrogen During Alumina Growth Below Yttria Nodules in FeCrAl(RE) at Low Partial Pressures of Water
Oxidation of FeCrAl(Re), when exposed to ∼35 ppm of water as sole supply of oxygen in predominantly nitrogen atmosphere, has two characteristic signatures. One is the internal nitridation owing to chromia nodules acting windows toward nitrogen permeation locally short-circuiting the protective α-Al2O3 scale. The second remarkable feature is the growth of thick, apparently defect-rich alumina scale under yttria-rich nodules. Hence, one part of the present study comprises exploratory DFT calculations to discriminate between the impacts of chromia and yttria viz. nitrogen permeation. The second part concerns boundary conditions for apparent rapid growth of alumina under yttria nodules. Yttria-associated surface energy stabilization of defect-rich alumina in presence of water was argued to involve hydrolysis-driven hydroxylation of said interface. Subsequent inward growth of the alumina scale was associated with outward diffusion of oxygen vacancies to be accommodated by the remaining proton producing a hydride ion upon surfacing at yttria-decorated alumina interfaces. The latter comprises the cathode process in a quasi-Wagnerian context. Two fates were discussed for this surface ion. One has H−–H+ recombination to form H2 at the interface in conjunction with OH– accommodation upon hydration, while the second allows hydrogen to be incorporated at VO sites in hydroxylated grain boundaries of the growing alumina scale. The latter was taken to explain the experimentally observed rapid oxide growth under yttria-rich nodules. Space charge due to proton reduction was proposed to cause transient inward cationic drag.
Publisher URL: https://link.springer.com/article/10.1007/s12678-017-0368-8
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